Aliphatic bis-dioxydiacetonitriles



Patented Aug. 12, 1947 ALIPHATIC BIS-DIOXYDIACETONITRILES Charles F. H.Allen and James A. Van Allan, Rochester, N. Y., aasignors to EastmanKodak Company, Rochester, N. Y., a corporation oi New Jersey No Drawing.Original application February 13,1?

1942, Serial No. 430,786.

Divided and this ap-" plication May 15, 1945, Serial No. 593,962

1 This invention relates to aliphatic dinitriles and to a process forpreparing them. This application is a division of our copendingapplication Serial No. 430,786, filed February 13, 1942.

Dinitriles of both the aliphatic and aromatic types have becomeincreasingly important, owing to the fact that diamines and dibasicacids are obtainable therefrom, both of which materials are used asstarting materials in the manufacture of polyamide resins of the nylontype. Moreover, in one method for manufacturing polyamide resins,dinitriles are employed as a starting material. A group of polyamideresins which possess very useful properties are those in which the chainof atoms between the amide groups contains one .or more oxygen atoms.However, the production of such polyamide resins has been retarded owingto the lack of a type of completely satisfactory starting materialswhich could be produced in relatively large quantities.

We have now found a new type of dinitrile.

containing two oxygen atoms between the nitrile groups. These dinitrilesgive rise to new dibasic acids, which are very well suited for theproduction of very useful polyamide resins. Moreover,

. these new dinitriles can be produced in large quantities.

It is, accordingly, an object of our invention to provide new dinitrilesand a process for preparing them. Still further objects will become 7apparent hereinafter.

, In accordance with our invention, we prepare dinitriles by reactingdihalides of the following general formula:

wherein n represents a positive integer of from two to ten and Xrepresents halogen, with a metal cyanide, such as cuprous cyanide.Silver,

or mercury cyanide can also be employed, The reaction is advantageouslyeffected in a nonaqueous medium e. g., benzene or toluene or otherhydrocarbon medium, The following examples will serve to illustrate ournew dinitriles and the process for preparing them.

Example 1.Ethylene-LZ-diOa'yacetOmitriZe NCCH2--O-CH2CH2OCH2CN 59.7 g.of cuprous cyanide were suspended in 4 Claims. (Cl. 260-464) 125 cc. ofbenzene contained in a 500 cc. threenecked flask equipp d with astirrer, reflux condenser and dropping funnel. The benzene suspensionwas heated to boiling on a steam bath and 89.7 g. ofethylene-.1,2-oxymethyl chloride were added from the dropping funnel tothe boiling suspension over a three-hour period, while stirring. Whenabout half of the chloride had been added, the reaction mixture suddenlybecame pasty and impossible to stir. The remainder of the chloride wasadded and the reaction mixture was refluxed for nine hours, At the endof this time, the benzene layer was decanted, the benzene removed andthe residue distilled. '7 to 8 g. of the dinitrile, boiling at 136 to137 C, at 2 mm. of mercury pressure, was obtained. Analysis: calculatedfor CsHaOzNz: N, 200; found N, 20.0.

Example 2.--,-Decamethylene--1,10-dioxymethyl nitrile NCCH2O(CH2)1oOCH2-CN 50 g. of cuprous cyanide were suspendedin 114 cc. of toluene.Th toluene suspension was heated to boiling and 67.5 g. ofdecamethylene- 1.10-oxymethyl chloride were slowly added to the boilingsuspension, with rapid stirring. The reaction mixture gradually becamebrown. After the addition of the chloride stirring and gentle boilingwere continued for 9 hours. The reaction mixture was cooled, the cuprouschloride filtered oif and washed with a little diethyl ether, the

ether washings being added to the toluene fil trate. The toluenefiltrate was treated to remove the ether and toluene and the residue wasdistilled at 6 mm. of mercury pressure. The yield of dinitrile was 87%,boiling point 219 to 220 0. Upon redistillation 50g. yield) of dinitrileboiling at 216 to 218 C. at 4 mm. of mercury pressure were obtained. Thedinitrile solidified vupon chilling. It was recrystallized from ethylalcohol (4 cc. per gram of nitrile) and obtained as white crystals,melting at 33 to 34 C. Analysis: calculated for C14H24O2N2: N, 11.1%;found: N, 10.8%.

Example 3.Hea:amethylene-1,6-dioa:ymethyl nitrile NCCH2O(CH2) sOCH2-CN40 g. of cuprous cyanide were suspended in 101) cc. of boiling toluene.To the boiling suspension were slowly added, with vigorous stirring,42.8 g. of hexamethylene 1,6 dioxymethyl chloride. After the addition ofthe chloride, gentle boiling and stirring were continued for 4.5 hours.The cuprous chloride was filtered off, the toluene removed from thetoluene filtrate and the residue distilled in vacuo. The yield ofdinitrile was 30 g. (76.5%), boiling point 205 to 208 C, at 20 mm. ofmercury pressure.

3 In a manner similar to that illustrated in the above examples,trimethylene-1,3-, tetramethylene-lA- pentamethylene-1,5-,heptamethylene- 1.6-, oct methylene-1,8- and nonamethylene-L9-dioxymethyl cyanide can be prepared. The alkylene bis oxymethyl halidesemploye in practicing our invention can'be prepared by reacting adihydric alcohol with formaldehyde Serial No.,312,722, filed January 6,1940.

The dinitrilesobtained in accordance with our invention can behydrolyzed, we have found, to give dibasic acids. The hydrolysis isadvantageously effected in the presence of alkali. such as an alkalimetal hydroxide for example. Mineral acids, such as hydrochloric andsulfuric, also accelerate the hydrolysis. The following examples willserve to illustrate our new dibasic acids and the manner of obtainingthem.

Example 4.DecamethyZene-1,10-diomuacetic acid 8 g. ofdecamethylene-l,lo-dioxymethyl nitrile were mixed with 15 cc. of 95%ethyl alcohol and 60 cc. of 20% aqueous sodium hydroxide. The mixturewas refluxed on the steam bath for 24 hours. The alcohol was thenevaporated and the residue allowed to cool. It solidified to a whitecrystalline mass. The mass was dissolved in 250 cc. of boiling water,the resulting solution filtered while hot and acidified withhydrochloric acid. The dioxyacetic acid crystallized from the acidifledsolution upon cooling. -It was filtered ofi, washed with a little coldwater. It was redissolved in 60 cc. of sodium carbonate solution, theresulting solution filtered and acidified with hydrochlori-c acid asbefore. The dioxyacetic acid was then recrystallized from heroin andobtained as white crystals melting at 84 to 86 C. Analysis:calculated'for CmHzeOp: C, 57.9; H, 9.0: found: C, 58.1; H, 9.0.

nide were mixed with 30 cc. of 95% ethyl alcohol and 120 cc. of 20%aqueous sodium hydroxide. The mixture was refluxed for 24 hours on asteam bath. The alcohol was then removed and the residue allowed tocool. 60 cc. of water were then added to the cool reaction mixturefollowed by 50 cc. of concentrated hydrochloric acid (sp. g. 1.18) withstirring. The resulting mixture was chilled and the dioxyacetic acidfllteredoff. The dioxyacetic acid was then dissolved in a minimum ofsodium carbonate solution, the resulting solution filtered and thedioxyacetic acidreprecipitated by hydrochloric acid. The dioxyaceticacid was recrystallized from hot water and obtained as white crystalsmelting at 92 to 94 C. Analysis: calculated for CmI-IaO: C, 51.3; H,7.7; found C, 51.4; H, 7.7.

In a manner similar to that shown in Examand hydrogen halide in anon-aqueous solvent,

. such as benzene. See our copending application ples 4 and 5,ethylene-1,2-, trimethylene-1,3-, tetramethylene-1,4-,pentamethylene-l,5-heptamethylene-1,7-, octamethylene-l,8- andnonamethylene-l,9-dloxyacetic acid can be prepared.

The dinitriles obtained in accordance with our invention can be made toundergo an, internal condensation to yield cyclic derivatives as shownin the following example.

E'kmmple 6.-1-cyano-4,1S-diczucuclopentadecanimide-(2) over a three-dayperiod, using a simplification of the Ziegler high dilution apparatus(Ziegler, Ann. 504, 122-125, 1933). After the addition of the hitrile,One liter of cold water was slowly added to the reaction mixture. Theethereal layer was then removed from the strongly alkaline aqueouslayer.

The ethereal layer was washed with hydrochloric acid (170 cc.concentrated hydrochloric acid diluted to 1500 cc.) to remove themethylaniline. The ether layer was decanted from a small amount ofinsoluble material. Upon distillation methyl aniline and naphthalenewere recovered. The residue was fractionally distilled and 19 g. ofimide boiling'at 155 to 167 C. at 1 mm. of mercury pressure wereobtained. The imide was recrystallized several times from ligroin togive 18 g. of white crystals melting at 69 to 71 C. Analysis: calculatedfor C14H2402N2: N, 11.1; found N, 11.1. I

What we claim as our invention and desire to be secured by LettersPatent of the United States eral formula:

:vheirein n represents a positive integer of from 2 2.Ethylene-l,2-dioxyacetonitrile. 3. Hexamethylene-1,6-dioxymethylnitrile. 4. Decamethylene-1,10-dioxymethyl nitrile.

j CHARLES F. H. ALLEN. JAMES A. VAN ALLAN.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,245,129 Greenwalt June 10, 19412,383,443 Bruson Aug. 28, 1945 2,169,578 Bruson et a1. Aug. 15, 1939 5Certificate of Correction I 6 v Patent No. 2,425,360. August 12, 1947.CHARLES F. H. ALLEN ET AL.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: Column 1,line 4, after the numeral 1942 and before the perlod insert ,(now UnitedStates Patent 2,388,813 dated November 13, 1945); and that the saidLetters Patent should be read with this correction therein that the samemay conform to the record of the case in the Patent Office.

Signed and sealed this 7th day of October, A. D. 1947.

THOMAS F. MURPHY,

Asez'sta'nt Uommz'ssioner of Patents.

